Aqueous particulate slurry compositions and methods of making same

ABSTRACT

A sand slurry composition and a method for making sand slurries are disclosed. The sand slurry composition is comprised of sand, an aqueous liquid and a chemical compound that renders the surface sand of hydrophobic. The method is comprised of rendering sand surface hydrophobic during or before making the slurry. This method and composition can find many applications in different industries, especially in various oil field applications.

This is a divisional application of U.S. application Ser. No. 12/595,461filed on Oct. 9, 2009, and which issued on Jan. 31, 2012 as U.S. Pat.No. 8,105,986. U.S. application Ser. No. 12/595,461 is a U.S. NationalStage under 35 U.S.C. §371 of international application numberPCT/CA2008/000669, filed on Apr. 11, 2008, currently expired.International application number PCT/CA2008/000669 claims priority fromCanadian Patent Application No. 2,585,065 filed Apr. 13, 2007, which iscurrently pending. All of the foregoing referenced documents areincorporated herein by reference in their entireties.

FIELD

This invention relates to particulate slurry compositions and methods ofmaking same in general, and sand slurries in particular.

BACKGROUND

Sand slurries are used in a variety of industries including petroleum,pipeline, construction and cleaning. One example of where large amountsof sand slurry are used in hydraulic fracturing for increasing oil andgas production. In a hydraulic fracturing process, a fracturing fluid isinjected through a wellbore into a subterranean formation at a pressuresufficient to initiate a fracture to increase oil and gas production.Frequently, particulates, called proppants, are suspended in thefracturing fluid and transported into the fracture as a slurry.Proppants include sand, ceramic particles, glass spheres, bauxite(aluminum oxide), and the like. Among them, sand is by far the mostcommonly used proppant. Fracturing fluids in common use include variousaqueous and hydrocarbon gels. Liquid carbon dioxide and nitrogen gas arealso used in fracturing treatments. The most commonly used fracturingfluids are aqueous fluids containing cross-linked polymers or linearpolymers to effectively transport proppants into formation. At the laststage of a fracturing treatment, fracturing fluid is flowed back tosurface and proppants are left in the created fracture to prevent itfrom closing back after pressure is released. The proppant-filledfracture provides a high conductive channel that allows oil and/or gasto seep through to the wellbore more efficiently. The conductivity ofthe proppant pack plays a dominant role in increasing oil and gasproduction. However it is well known that polymer residues from thefracturing fluid greatly reduce the conductivity of the proppant-pack.

The density of sand is about 2.6 g/cm³ while the density of water is 1g/cm³. The large density difference between sand and water makes sandsettle quickly in water, even under conditions of high water turbulence.Once settled, sand is not easily lifted by the flow of the aqueousliquid in which it has settled.

Conventionally, to make a relatively stable slurry under static or/anddynamic conditions, sand is commonly suspended in a viscoelastic fluid.In viscoelastic fluids, yield stress plays a dominant role in suspendingthe particles. Yield stress is the minimum shear stress required toinitiate flow in a viscoelastic fluid. Basically, the viscosity of thefluid works to slow down the rate of particle settling, while the yieldstress helps to suspend the particles. Under dynamic conditions,agitation or turbulence further help stabilize the slurry. Therefore, tomake stable and cost-effective sand slurries, conventional methods focuson manipulating the theological properties of the fluid by adding asufficient amount of viscosifier, for example, a natural or syntheticpolymer, into the slurry. It is not unusual that a polymer is usedtogether with a foaming agent to improve the rheology and to reduce thecost.

In some applications, for example, well cleanout and sand cleanout inpipe lines, where slurries have to be made in situ to carry the sandout, the presence of a viscosifier in the liquid medium normally hasdetrimental effect. This is mainly due to the fact that turbulent flowplays a critical role in transporting sand in these situations while aviscosifier tends to suppress the turbulence.

Flotation has been used in minerals engineering for the separation offinely ground valuable minerals from other minerals. Crude ore is groundto fine powder and mixed with water, collecting reagents and,optionally, frothing reagents. When air is blown through the mixture,hydrophobic mineral particles cling to the bubbles, which rise to formfroth on the surface. The waste material (gangue) settles to the bottom.The froth is skimmed off, and the water and chemicals are removed,leaving a clean concentrate, The process, also called thefroth-flotation process, is used for a number of minerals.

The primary mechanism in such a flotation process is the selectiveaggregation of micro-bubbles with hydrophobic particles under dynamicconditions to life the particles to the liquid surface. The minerals andtheir associated gangue usually do not have sufficient hydrophobicity toallow bubbles to attach. Collecting agents, known as collectors, arechemical agents that are able to selectively adsorb to desired mineralssurfaces and make them hydrophobic to permit the aggregation of theparticles and micro-bubbles and thus promote separation. Frothers arechemical agents added to the mixture to promote the generation ofsemi-stable froth. In the so-called reverse flotation process, theundesired minerals, such as silica sand are floated away from thevaluable minerals which remain in the tailings. The reverse flotation ofsilica is widely used in processing iron as well as phosphate ores.

A wide variety of chemical agents are useful as collectors and frothersfor flotation of silica particles. Amines such as simple primary andsecondary amines, primary ether amine and ether diamines, tallow aminesand tall oil fatty acid/amine condensates are known to be usefulcollectors for silica particles. It is well established that thesechemical compounds strongly adsorb to sand surface and change the sandsurface from hydrophilic to hydrophobic. In fact, the reason that thesecompounds are used as collectors is because of their capability ofhydrophobising sand surface to allow form stable sand/bubblesaggregations. The preferred collectors are amine collectors having atleast about twelve carbon atoms. These collectors are commerciallyavailable from, for example, Akzo Nobel or Tomah Products Inc. Otherpossible collectors are oleate salts which normally need presence ofmultivalent cations such as Ca++ or Mg++ to work effectively.

Compounds useful as frothers include low molecular weight alcoholsincluding methyl isobutyl carbinol and glycol ethers.

Such flotation methods are not used in making sand slurries, andespecially in making sand slurries for various oil field applications.

SUMMARY

According to one embodiment, the present invention relates to a slurrycomposition including a particulate, an aqueous medium and a collectorwhich renders the surface of the particulate hydrophobic, and a methodof making the same

The present invention in another embodiment relates to a slurrycomposition including a particulate, an aqueous medium and a collectorwhich renders the surface of the particulate hydrophobic, and a frother,and a method of making the same.

The present invention in a further embodiment relates to a slurrycomposition which can be made in situ, under dynamic conditions or“on-the fly”.

In a still further embodiment, the present invention relates to a wellservice fluid composition comprising a particulate, an aqueous medium,and a collector which renders the surface of the particulatehydrophobic. The fluid can further include a frother. The fluid canfurther include a surfactant. The proppant can be sand.

DESCRIPTION OF THE INVENTION

In the present invention, attention is turned away from the rheology ofthe liquid medium containing the sand, and instead focused on the sand.While in each case the characteristics of sand (in this embodimentnamely its size distribution and density) are constants, the presentinvention is directed to improving slurry fluidity and stability by“lifting” the sand instead of suspending the sand by the liquid medium.

In one embodiment, the lift is achieved by attaching micro-bubbles ofsufficient stability to the sand surface. Alternatively, cavities arecreated among neighboring sand grains. The micro-bubbles or cavitiesattached to the sand surfaces help lift the sand up, due to theincreased buoyancy.

In the present invention, the basic principle of reverse flotation isapplied to the preparation of aqueous sand slurries for transportingsand, which have wide applications, especially in oil field. Theseapplications include hydraulic fracturing, drilling, wellbore cleanout,sand cleanout in pipeline and sand jetting. Sand used in theseapplications typically range in size from 10 to abut 100 mesh. All theseapplications are carried out under dynamic conditions, where turbulencenormally exists.

In the present invention, the surface of sand grains, which are stronglyhydrophilic, are modified to become hydrophobic to allow aggregationwith micro-bubbles in an aqueous liquid (including water, brines, andwater containing small amounts of alcohols or other organic solvents)under dynamic conditions. The aggregation with bubbles provides sandwith increased buoyancy and therefore greatly improves the fluidity andstability of the slurry, without employing a viscosifier.

There are different ways to make particulate slurries according to thepresent invention. For example, a particulate such as sand can be firsttreated with a collector in water, dried and then mixed with water underdynamic conditions to make slurry for later applications. Or theparticulate slurry can be prepared “on-the-fly”, i.e., sand, acollector, and water are mixed together, under dynamic conditions. Orthe slurry can be prepared in situ, where sand is mixed with watercontaining a collector under dynamic conditions, for example, inwellbore cleanout and sand cleanout in pipeline, where liquid flow ofhigh rate is normally applied.

In addition to the collectors, different furthers can also be added toenhance the fluidibility and the stability of the slurry. Frothersinclude methyl isobutyl carbinol, hexyl alcohol and glycol ethers. Inaddition to a collector, a conventional surfactant, which itself is notnormally used as a collector, may also be added to enhance the flotationof the sand. However, any added surfactants must be compatible with thecollector. For example, a surfactant should not form precipitation witha collector, and should not reduce the surface tension significantly toallow the hydrophobic sand be sufficiently wetted by the aqueous medium.Otherwise, micro-bubbles are not able to form stable aggregations withthe hydrophobic sands.

Collectors useful in the present invention are amines including simpleprimary and secondary amines, primary ether amine and ether diamines,tallow amines and tallow oil fatty acid/amine condensates. Examples ofsuch collectors include propanamine, 3-nonyloxy-; 1,3-propanediamine,N-tridecyloxy-3,1-propanediyl-; the condensate of diethylenetetraamineand tallow oil fatty acid, C₁₆-C₁₈ tallow amine, decylamine,dodecylamine, dihexyl amine, tetradecyloxypropyl amine, dodecyloxypropylamine, octadecyl/hexadecyloxypropyl amine, isododecyloxypropyl amine,isotridecyloxypropyl amine, dodecyl-1,3-propanediamine,hexadecyl-1,3-propanediamine, tallow-1,3-propanediamine and thecondensate of an excess of fatty acids with diethanolamine. Alkanolamines with short carbon chains, such as C₁₋₆ alkanol amines, or shortcarbon chain amine such as hexylamine can also be combined with longcarbon chain amine collectors to enhance the flotation. Such collectorsand related compositions for silica are well known in the art. Moredetails can be found in U.S. Pat. Nos. 2,312,387; 2,322,201; 2,710,856;4,234,414; and 5,124,028; S. Takeda and S. Usui in Colloid and Surfaces,29, 221-232, 1988; and J. L. Scott and R. W. Smith in MineralsEngineering, Vol. 4. No, 2, 141-150, 1991. which are incorporated hereinby reference.

Particulate slurries according to the present invention can be preparedat the surface or under a subterranean formation in situ whereparticulates, an aqueous fluid, and a collector, such ashexadecyl-1,3-propanediamine are mixed together. Additionally, afrother, for example, hexyl alcohol can also be added together with acollector into the slurry. Or the particulates can be first mixed with afluid and a collector and then drying up the liquid. The treatedparticulates can be subsequently slurred.

The amount of collector needed generally depends on the sandconcentration and size. Normally, the amount of a collector added is inthe range of 0.01 g/kg to 1 g/kg sand. For example, during a fracturingoperation, a collector can be added into water and mixed with sand asslurry under high pumping rate to transport sand into formation. In somecases, a friction reducing agent, for example, a small amount of a watersoluble polymer, can also be added into the slurry to reduce frictionpressure. It should be noted that the friction reducing agent should notform precipitation with the collector or reduce significantly theformation of bubble-sand aggragations. Optionally, nitrogen or carbondioxide gas can be mixed into the slurry. Similarly in wellbore sandcleanout, water containing the collector is mixed with sand in situ athigh flow rate and carries the sand out the wellbore efficiently.Optionally, nitrogen or carbon dioxide gas can be mixed with the fluid.

The following provides several non-limiting examples of the presentinvention.

EXAMPLE 1

100 ml of water and 50 grams of 30/50 US mesh fracturing sands wereadded into each of two glass bottles (200 ml). 0.07 ml of Armeen DMTD, atallowalkyl-dimethyl amine from Akzo Nobel, was added into one of thebottles and the other bottle was used as control. The bottles werevigorously shaken and then let stand to allow sands settle down. Whilethere are no bubbles observed in the control one, bubbles are attachedto the sand grains in the one containing Armeen DMTD, and moreover therewere a layer of sands floating on the top. The volumes of the settledsands in the two bottles were compared. In the bottle containing ArmeenDMTD, the volume of the settled sands was about 20 percent greater thanthe one without, and the sands are more fluid. Bubbles are attached tothe sand grains. When the bottles were tilted slowly, the settled sandsin the control tended to move as individual sand grains, while thesettled sands containing Armeen DMTD tended to move as cohesive masses.

EXAMPLE 2

100 ml of water and 50 grams of 30/50 US mesh fracturing sands wereadded into each of two glass bottles (200 ml). 0.07 ml of Armeen DMTD, atallowalkyl-dimethyl amine from Akzo Nobel, and 0.05 ml of TEGO Betaine810, capryl/capramidopropyl betaine, an amphoteric hydrocarbonsurfactant from Degussa Corp., were added into one of the bottles andthe other bottle was used as control. The bottles were vigorously shakenand then let stand to allow sands settle down. While there are nobubbles observed in the control one, bubbles are attached to the sandgrains in the one containing Armeen DMTD, and moreover there were alayer of sands floating on the top. The volumes of the settled sands inthe two bottles were compared. In the bottle containing Armeen DMTD, thevolume of the settled sands was about 20 percent greater than the onewithout, and the sands are more fluid. Bubbles are attached to the sandgrains. When the bottles were tilted slowly, the settled sands in thecontrol tended to move as individual sand grains, while the settledsands containing Armeen DMTD tended to move as cohesive masses.

EXAMPLE 3

100 ml of water and 50 grams of 30/50 US mesh fracturing sands wereadded into each of two glass bottles (200 ml). 0.05 ml of Armeen DMTD, atallowalkyl-dimethyl amine from Akzo Nobel, and 0.3 ml of hexyl alcoholwere added into one of the bottles and the other bottle was used ascontrol. The bottles were vigorously shaken and then let stand to allowsands settle down. While there are no bubbles observed in the controlone, bubbles are attached to the sand grains in the one containingArmeen DMTD, and moreover there were a layer of sands floating on thetop. The volumes of the settled sands in the two bottles were compared.In the bottle containing Armeen DMTD, the volume of the settled sandswas about 50 percent greater than the one without, and the sands aremore fluid. When the bottles were tilted slowly, the settled sands inthe control tended to move as individual sand grains, while the settledsands containing Armeen DMTD tended to move as cohesive masses.

I claim:
 1. A method of preparing a fracturing slurry composition for afracturing operation comprising mixing together: a. sand proppants, b.water, c. a collector which renders the surface of the proppantshydrophobic, and d. a gas, wherein the collector is selected from agroup consisting of a primary amine, a secondary amine, a tertiaryamine, a primary ether amine, an ether diamines, a tallow amine, and atallow oil fatty acid/amine condensate; and wherein bubbles are attachedto the sand surfaces under dynamic conditions.
 2. The method accordingto claim 1 wherein the collector is a primary amine containing at leasttwelve carbon atoms.
 3. The method according to claim 1 wherein thecollector is a secondary amine containing at least twelve carbon atoms.4. The method according to claim 1 wherein the collector is selectedfrom a group consisting of propanamine, 3-nonyloxy-; 1,3-propanediamine,N-tridecyloxy-3,1-propanediyl-; the condensate of diethylenetetraamineand tallow oil fatty acid, tallow amine, tallowalkyl-dimethyl amine,decylamine, dodecylamine, dihexyl amine, tetradecyloxypropyl amine,dodecyloxypropyl amine, octadecyl amine, hexadecyloxypropyl amine,isododecyloxypropyl amine, isotridecyloxypropyl amine, hexadecylamine,dodecyl- 1,3-propanediamine, hexadecyl-1,3-propanediamine,tallow-1,3-propanediamine, the condensate of an excess of fatty acidwith diethanolamine and an oleate salt.
 5. The method according to claim1 further comprising a frother.
 6. The method according to claim 5wherein the frother is an alcohol.
 7. The method according to claim 5wherein the frother is selected from a group consisting of a hexylalcohol, a methyl isobutyl carbinol, a glycol ether and a combinationthereof.
 8. The method according to claim 1 wherein the gas is selectedfrom a group consisting of air, nitrogen and carbon dioxide.
 9. Themethod according to claim 1 wherein the collector is at a concentrationin the range of about 0.1 g/kg to 1 g/kg of proppant.
 10. The methodaccording to claim 1 further comprising a friction reducing agent. 11.The method according to claim 1 wherein the collector is a tallow amine.12. The method according to claim 1 wherein the collector is anoctadecyl amine.
 13. The method according to claim 1 wherein thecollector is a tallowalkyl-dimethyl amine.
 14. The method according toclaim 1 wherein the fluid composition is prepared in an undergroundformation.
 15. A method of making an aqueous fracturing slurrycomposition for hydraulic fracturing operation comprising: a. contactingsand proppant with a medium containing a collector to render theproppant hydrophobic; b. separating the proppant from the medium, c.mixing the treated proppants under dynamic conditions, with water undershear in the presence of a gas; and wherein the collector is selectedfrom a group consisting of a primary amine, a secondary amine, atertiary amine, a primary ether amine, an ether diamines, a tallowamine, and a tallow oil fatty acid/amine condensate; and wherein bubblesare attached to the sand surfaces under dynamic conditions.
 16. Themethod of claim 15 wherein the collector is a primary amine containingat least twelve carbon atoms.
 17. The method of claim 15 wherein thecollector is a secondary amine containing at least twelve carbon atoms.18. The method of claim 15 wherein the collector is selected from agroup consisting of propanamine, 3-nonyloxy-; 1,3-propanediamine,N-tridecyloxy-3,1-propanediyl-; the condensate of diethylenetetraamineand tallow oil fatty acid, tallow amine, tallowalkyl-dimethyl amine,decylamine, dodecylamine, dihexyl amine, tetradecyloxypropyl amine,dodecyloxypropyl amine, octadecyl amine, hexadecyloxypropyl amine,isododecyloxypropyl amine, isotridecyloxypropyl amine, hexadecylamine,dodecyl-1,3-propanediamine, hexadecyl-1,3-propanediamine,tallow-1,3-propanediamine, the condensate of an excess of fatty acidwith diethanolamine and an oleate salt.
 19. The method of claim 15wherein the collector is a tallow amine.
 20. The method of claim 15wherein the collector is an octadecyl amine.
 21. The method of claim 15wherein the collector is a tallowalkyl-dimethyl amine,
 22. The method ofclaim 15 wherein the gas is selected from a group consisting of air,nitrogen and carbon dioxide.
 23. The method of claim 15 wherein thecomposition further comprising a friction reducing agent.
 24. The methodaccording to claim 1 wherein the collector is a primary amine containingat least eighteen carbon atoms.
 25. The method according to claim 1wherein the collector is a secondary amine containing at least eighteencarbon atoms.
 26. The method according to claim 1 wherein the collectoris a tertiary amine containing at least eighteen carbon atoms.
 27. Themethod according to claim 15 wherein the collector is a primary aminecontaining at least eighteen carbon atoms.
 28. The method according toclaim 15 wherein the collector is a secondary amine containing at leasteighteen carbon atoms.
 29. The method according to claim 15 wherein thecollector is a tertiary amine containing at least eighteen carbon atoms.